CN109588044B

CN109588044B - System for detecting abnormality of carbon dioxide separation membrane device

Info

Publication number: CN109588044B
Application number: CN201880002793.7A
Authority: CN
Inventors: 金东燮; 李正彬; 李仲远; 申起荣; 金宽植
Original assignee: East West Power Generation In South Korea; South East Power Generation Unit; Style Commune Astro Rome; Han Guodianligongshe; Korea Western Power Co Ltd
Current assignee: East West Power Generation In South Korea; South East Power Generation Unit; Style Commune Astro Rome; Han Guodianligongshe; Korea Western Power Co Ltd
Priority date: 2017-07-28
Filing date: 2018-01-05
Publication date: 2021-08-20
Anticipated expiration: 2038-01-05
Also published as: WO2019022322A1; US11000801B2; US20190366264A1; PH12019500057A1; CN109588044A; PH12019500057B1; KR101919302B1

Abstract

The invention relates to a method for producing carbon dioxide (CO)₂) An abnormality detection system for a separation membrane device, comprising: an inlet unit comprising CO₂Through which the gas comprising CO enters₂Means for separating the membrane modules; a separation membrane module comprising an inlet for containing CO₂To each CO₂Separating the membrane module and permeating the supplied gas through CO₂Separating the membranes and separately passing the gas having relatively high CO that has permeated through the membranes₂The concentrated gas is discharged to a first discharge port, and the gas having relatively low CO that does not permeate through the separation membrane is discharged₂The gas with the concentration is discharged to a second discharge port; a permeation unit for discharging a gas having a relatively high CO content₂A concentrated gas discharged from the separation membrane module to the outside of the apparatus; residue unit for discharging residue with relatively low CO₂A concentrated gas discharged from the separation membrane module to the outside of the apparatus; a measurer for measuring flow rate, CO, in the unit including the inlet unit, the infiltration unit and the residue unit₂Concentration and pressure information; and a controller determining the existence of an abnormality from the information collected by the measurer, wherein the controller determines whether the apparatus is in an abnormal situation.

Description

System for detecting abnormality of carbon dioxide separation membrane device

Technical Field

The invention relates to a method for producing carbon dioxide (CO)₂) An abnormality detection system for a separation membrane device.

Background

Worldwide efforts are being made to reduce carbon dioxide (CO)₂) To reduce rapid climate change due to global warming. Accordingly, there is an increasing demand for Carbon Capture and Sequestration (CCS) technology that can capture CO from flue gases produced from the combustion of fossil fuels₂。

Conventional CCS technologies include: absorption techniques in which the exhaust gas is contacted with a chemical carbon dioxide absorbent such as amine, ammonia or potassium carbonate; absorption techniques such as Pressure Swing Adsorption (PSA) and Temperature Swing Adsorption (TSA) in which a temperature difference or a pressure difference is used to pass the off-gas through an absorbent; and a low temperature technique of selectively cooling and condensing a target gas using a vapor pressure difference according to a kind of the gas. However, such conventional CCS technology has high energy consumption and has significant limitations in terms of processing power or facility repair.

One of the newly developed CCS technologies is CO₂Separation membrane apparatus capable of separating CO from exhaust gas produced in coal-fired power plant at low cost and high efficiency₂。CO₂The separation membrane uses the size difference and permeability difference of gas molecules contained in the exhaust gas and the polarity difference of the separation membrane module to separate and capture CO in the exhaust gas₂。

Usually, CO₂The separation membrane facility uses a module unit in which a separation membrane material and a support or the like are combined in an internal pressure vessel, and an injected gas is passed through the internal pressure vessel to capture CO₂And then CO is discharged₂And filtering the gas. CO 2₂The separation membrane apparatus can expand the apparatus and the processing capacity in a relatively easy manner by increasing the number of separation membranes or modules according to the operating conditions and the separation performance target.

In addition, CO₂The advantage of the separation membrane device is that it is very energy efficient, since in CO₂It does not involve phase changes during the separation process; it is environmentally friendly because it does not discharge harmful substances in the air and does not discharge waste water; for CO₂The separation membrane device installation equipment and facilities are relatively easy because it is in the form of a module; and its application can be extended to other than CO₂Other fields of gas capture technology than capture processes such as gas refining.

However, due to CO₂Separation membrane equipment is a recently introduced technology, and thus there is not much CO in a real power plant₂The application and commercialization of separation membrane devices. Therefore, there is a great need for continuous research and technical development for CO₂Efficient operation of a separation membrane device.

For example, in similar technical fields such as water treatment separation membranes and methane/nitrogen separation membranes that have been commercialized, since a plant must be commissioned in order to obtain appropriate operating conditions according to the performance of an installed separation membrane, and then the resulting value must be changed while continuously monitoring on site, there is a problem in that: there are inconveniences in that many tests and errors have to be experienced, it is difficult to predict whether an abnormality occurs in the equipment according to a change in operating conditions, and it is difficult to accurately check a place or a time point where an abnormal situation occurs.

In addition, in CO₂In the case of a separation membrane apparatus, since the response speed thereof is higher than that in the similar technical field, it is important to quickly detect or predict an abnormality in a separation membrane.

Thus, with respect to operating CO₂In the method of the separation membrane apparatus, there is an increasing need to develop a method capable of detecting or predicting an abnormality such as a point of time at which an operation method should be changed, whether a separation membrane needs to be cleaned, and whether a separation membrane module is damaged and needs to be replaced.

Disclosure of Invention

Technical problem

One aspect of the present invention provides a carbon dioxide (CO)₂) Separation membrane device abnormality detection system capable of accurately checking CO in which an abnormal situation has occurred₂The region of the separation membrane apparatus or the time point at which an abnormal condition has occurred, so that it is possible to quickly detect the suitability of the operation when the operation method is changed, to quickly detect whether the separation membrane needs to be cleaned, and to quickly detect the time period during which the damaged module should be replaced.

Technical scheme

One embodiment of the present invention relates to a carbon dioxide (CO)₂) An abnormality detection system for a separation membrane device, comprising: an inlet unit comprising CO₂Through which the gas comprising CO enters₂Means for separating the membrane modules; a separation membrane module comprising an inlet for containing CO₂To each CO₂Separating the membrane module and permeating the supplied gas through CO₂Separating the membranes and respectively permeating through the membranes with a relatively high CO content₂The concentrated gas is discharged to a first discharge port, and the gas having relatively low CO that does not permeate through the separation membrane is discharged₂The gas with the concentration is discharged to a second discharge port; a permeation unit for discharging a gas having a relatively high CO content₂A concentrated gas is divided intoDischarging the separated membrane assembly to the outside of the equipment; residue unit for discharging residue with relatively low CO₂A concentrated gas discharged from the separation membrane module to the outside of the apparatus; a measurer for measuring flow rate, CO, in the unit including the inlet unit, the infiltration unit and the residue unit₂Concentration and pressure information; and a controller determining whether there is an abnormality by the information collected by the measurer; wherein when the first reference value calculated using the following equation 1 is about less than 95%, the controller monitors the operation condition of the plant as an abnormal condition, and when the first reference value calculated using the following equation 1 is about more than 95% or higher, the controller calculates the second reference value and the third reference value according to the following equation 2 and equation 3 to determine the operation state of the plant:

[ equation 1]

First reference value [ { (Q) [ ]_P×C_P·CO2)+(Q_R×C_R·CO2)}/(Q_IN×C_IN·CO2)]×100

[ formula 2]

Second reference value ═ J- { (Q)_P×C_P·CO2)/(Q_IN×C_IN·CO2)×100}│

[ formula 3]

Third reference value ═ K-C_P·CO2│，

Wherein, in formula 1 to formula 3:

Q_INindicating the CO content entering the apparatus through the inlet unit₂Flow rate (Nm) of gas³/hr)；

Q_PIndicates the flow rate (Nm) of the gas discharged to the permeation cell³/hr)；

Q_RShows the flow rate (Nm) of the gas discharged to the residue unit³/hr)；

C_IN·CO2Indicating CO in the inlet unit₂Concentration (% by volume);

C_P·CO2CO representing gas discharged to the permeation unit₂Concentration (% by volume);

C_R·CO2CO representing gas discharged to the residue unit₂Concentration (volume%))；

J represents target CO₂Capture rate (%); and

k represents the target CO₂Concentration (% by volume).

Advantageous effects

The invention can provide carbon dioxide (CO)₂) Separation membrane device abnormality detection system capable of accurately checking CO in which an abnormal situation has occurred₂The region of the separation membrane apparatus or the time point at which an abnormal condition occurs, so that it is possible to quickly detect the suitability of the operation when the operation method is changed, to quickly detect whether the separation membrane needs to be cleaned, and to quickly detect the time period during which the damaged module should be replaced.

Drawings

FIG. 1 shows carbon dioxide (CO) according to one embodiment of the present invention₂) A schematic flow diagram of a separation membrane device anomaly detection system.

FIG. 2 shows an exemplary CO according to an embodiment of the present invention₂A separation membrane device.

FIG. 3 shows a CO according to an embodiment of the invention₂Exemplary cross-sections (designated areas) of the separation membrane device.

FIG. 4 shows the passage of CO as pressure changes according to one embodiment of the present invention₂Separation membrane plant anomaly detection system predicting CO in a permeation unit₂Results of the change in concentration.

FIG. 5 illustrates the passage of CO as pressure changes according to one embodiment of the present invention₂Separation membrane plant anomaly detection system predicting CO in a permeation unit₂Results of varying values of flow rate.

FIG. 6 illustrates the passage of CO as the flow rate varies according to one embodiment of the present invention₂Separation membrane plant anomaly detection system predicting CO in a permeation unit₂Results of the change in concentration.

FIG. 7 shows the passing of CO as the flow rate is varied according to one embodiment of the present invention₂Separation membrane plant anomaly detection system predicting CO in a permeation unit₂Results of varying values of flow rate.

Detailed Description

One embodiment of the present invention relates to a carbon dioxide (CO)₂) An abnormality detection system for a separation membrane device, comprising: an inlet unit comprising CO₂Through which the gas comprising CO enters₂Means for separating the membrane modules; a separation membrane module including an inlet for introducing CO₂To each CO₂Separating the membrane module and permeating the supplied gas through CO₂Separating the membranes and respectively permeating through the membranes with a relatively high CO content₂The concentrated gas is discharged to a first discharge port, and the gas having relatively low CO that does not permeate through the separation membrane is discharged₂The gas with the concentration is discharged to a second discharge port; a permeation unit for discharging a gas having a relatively high CO content₂A concentrated gas discharged from the separation membrane module to the outside of the apparatus; residue unit for discharging residue with relatively low CO₂A concentrated gas discharged from the separation membrane module to the outside of the apparatus; a measurer for measuring flow rate, CO, in the unit including the inlet unit, the infiltration unit and the residue unit₂Concentration and pressure information; and a controller determining whether there is an abnormality by the information collected by the measurer; wherein the controller monitors the operation condition of the equipment as an abnormal condition when the first reference value calculated using formula 1 of the present invention is about less than 95%, and calculates the second reference value and the third reference value to determine the operation state of the equipment according to formula 2 and formula 3 of the present invention when the first reference value calculated using formula 1 is about more than 95% or higher.

In this way, the present invention can accurately check CO₂An area of an abnormal situation having occurred or a time point of an abnormal situation having occurred in the separation membrane apparatus, so that it is possible to quickly detect suitability of an operation when an operation method is changed, to quickly detect whether it is necessary to clean the separation membrane, and to quickly detect a time period during which a damaged module should be replaced.

For example, CO of the present invention₂The abnormality detection system of the separation membrane equipment can be applied to the flat-plate type separation membraneCO of the module₂A separation membrane module. In this case, the effect of applying the abnormality detection method can be further enhanced.

FIG. 2 illustrates CO including an exemplary separation membrane module to which the present invention is applicable₂A separation membrane device. Referring to FIG. 2, CO-containing gas discharged from a boiler of a coal-fired power plant or the like₂Is introduced into the apparatus via the inlet unit 100 and is then fed along a duct to the modules and the separation membranes within the modules via the injection ports of the first module 10. In this case, CO₂The

separation membrane modules

10, 20, and 30 may include two or

more unit modules

11, 12, and 13, such as the first module 10 shown in fig. 2, or may be modules each formed of a single unit module, such as the second module 20 and the third module 30 shown in fig. 2. As shown in FIG. 2, the CO-containing gas to be injected via the inlet unit 100₂Is separated into the gas having relatively high CO by the first to third modules₂A gas of concentration and having a relatively low CO₂A concentration of gas. In this case, the permeate unit with the relatively high CO that is finally discharged to the plant has₂Concentration of gas (captured CO)₂Gas) can include, for example, CO of about 80% or greater purity, about 90% or greater purity, or about 96% or greater purity (or about 80% or greater concentration by volume, about 90% or greater concentration by volume, or about 96% or greater concentration by volume)₂And the gas may be discharged to a processing device, a storage device, etc. outside the apparatus via the permeation unit 200. In addition, the final separated in the plant has relatively low CO₂The gas of concentration may be discharged to the outside through the residue unit 300 (formed separately from the infiltration unit 200), or may be supplied (circulated) to the first to third modules again through the injection ports. In this case, the apparatus may permeate the target CO of the unit₂The concentration K is set to, for example, about 90% by volume or more or about 96% by volume or more, and the target CO of the permeation unit can be set₂The capturing rate J is set to, for example, about 90 vol% or more or about 96 vol% or more, and these set values may be input into the system and it is determined whether there is an abnormality in the operation using equations 1 to 3 using the input set values.

The order and configuration of the condenser and the cooler shown in fig. 2 may be freely changed and are not limited to those shown in fig. 2. The configuration of the apparatus is not limited to the configuration shown in fig. 2. The plant may be arranged in various ways such that energy consumption can be minimized and the target CO achieved in view of optimal arrangement of separation membrane modules and recirculation in the process₂Capture Rate and target CO₂And (4) concentration.

CO of the invention₂The separation membrane device abnormality detecting system includes a measurer (not shown) for measuring information including flow rates, CO, in the inlet unit 100, the permeation unit 200, and the residue unit 300₂Concentration and pressure; and a controller (not shown) for determining the presence of an abnormality based on the information collected by the measurer.

The controller detects the operation condition of the apparatus as an abnormal condition when the first reference value calculated using the following equation 1 is about less than 95%. In this case, the system can solve the abnormal situation by performing an operation of checking whether a leak has occurred in the piping of the apparatus and checking whether the apparatus has reached a normal state.

[ equation 1]

In formula 1, Q_INIndicating the CO content entering the apparatus through the inlet unit₂Flow rate of gas (Nm)³/hr); QP represents the flow rate of gas discharged to the permeation unit (Nm)³/hr)；Q_RShows the flow rate (Nm) of the gas discharged to the residue unit³/hr)；C_IN·CO2Indicating CO in the inlet unit₂Concentration (% by volume); c_P·CO2CO representing gas discharged to the permeation unit₂Concentration (% by volume); c_R·CO2CO representing gas discharged to the residue unit₂Concentration (% by volume).

Flow rate and CO₂Each of the concentrations may be measured by a measurer disposed in an area (e.g., an inlet unit, a permeation unit, or a residue unit) in which the corresponding factor is measured.

When the first reference value calculated using equation 1 is about 95% or more, the controller calculates the second reference value and the third reference value according to equation 2 and equation 3 below to determine the operation state of the device.

[ formula 2]

Second reference value ═ J- { (Q)_P×C_P·CO2)/(Q_IN×C_IN·CO2)×100}│

[ formula 3]

Third reference value ═ K-C_P·CO2│

In equations 2 and 3, Q_IN、Q_P、Q_R、C_IN·CO2、C_P·CO2And C_R·CO2As described above, J represents the target CO₂Capture (%), and K represents the target CO₂Concentration (% by volume).

Target CO₂Capture ratio (J) and target CO₂The density (K) is a value set as a device operation target by a user, and is not limited to the above. For example, target CO₂The capture rate (%) may be set to about 90% or more, about 95% or more, about 96% or more, or about 99% or more, and the target CO₂The concentration (% by volume) may be set to about 90% by volume or more, about 95% by volume or more, about 96% by volume or more, or about 99% by volume or more.

The controller may determine that the CO is not greater than a set value specified by the user when the first reference value calculated using equation 1 is 95% or more and the second reference value calculated using equation 2 and the third reference value calculated using equation 3 are less than or equal to the set value specified by the user₂And (4) normally operating the separation membrane device. In this case, CO₂The separation membrane device abnormality detection system may periodically monitor the CO by recalculating the first to third reference values at predetermined time intervals₂A separation membrane device. The recalculation time interval may be set differently according to the user's determination. For example, the recalculation time interval may be a time interval of about five minutes to about thirty minutes, but is not limited thereto.

The controller may determine the operation state of the apparatus as an abnormal condition when the first reference value calculated using equation 1 is about less than 95% and one or more of the second reference value calculated using equation 2 and the third reference value calculated using equation 3 exceeds a set value designated by a user. In this way, the presence of an abnormality in operation can be detected quickly, and the second reference value and the third reference value can be used to implement countermeasures for solving the abnormal operation, as described below.

The abnormal operation detection using the second reference value and the abnormal operation detection using the third reference value may be performed simultaneously or sequentially. In this case, the order of detection is not limited.

The set value designated by the user refers to a value arbitrarily set by the user corresponding to the actual operation state. As the setting value designated by the user becomes smaller, the device operation can be performed more accurately. However, when the detection and determination of the presence of an abnormality are performed sensitively, system operation efficiency may be reduced. Thus, the user-specified set point may specifically be about 10% or less, more specifically about 5% or less, such as 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, and 1%. When the setting value designated by the user is within the above range, the system operation efficiency can be improved.

When one or more of the second reference value calculated using formula 2 and the third reference value calculated using formula 3 exceeds a set value designated by a user, the controller may divide the entire apparatus into two or more regions and then calculate a fourth reference value based on formula 4 of the present invention, determining whether an abnormal situation has occurred per region for each region.

In a particular embodiment, when the first reference value is less than about 95%, the CO₂The separation membrane device abnormality detection system may omit the process of calculating the second reference value and the third reference value, and then immediately perform a countermeasure against the abnormal operation. In this case, a suitable countermeasure may be to detect and repair a leak portion of the entire pipe included in the apparatus and to check whether the apparatus has reached a normal state, but is not limited thereto.

In another embodiment, when the first reference value is about 95% or moreHigh time, CO₂The separation membrane device abnormality detection system may sequentially perform a process of calculating the second reference value and the third reference value and detect an abnormal operation. In this case, when both the second reference value calculated using equation 2 and the third reference value calculated using equation 3 are less than or equal to the set value designated by the user, CO₂The separation membrane device abnormality detection system may determine that the operation state of the device is normal, and recalculate the first reference value at intervals of about 5 minutes to 30 minutes.

In yet another embodiment, the CO is when the first reference value is about 95% or more and one or more of the second reference value and the third reference value exceeds a user-specified set point₂The separation membrane device abnormality detection system may determine the operation state of the device as abnormal, divide the entire device into two or more regions, and then determine whether an abnormal condition has occurred in each region.

To determine if an abnormal situation has occurred in a region, CO₂The separation membrane device abnormality detection system divides the device into two or more regions. The standard for the division apparatus is not particularly limited, and may be executed by a unit advantageous for detecting an abnormal operation. For example, as described above in fig. 2, the apparatus setup may be divided into sections (apparatus areas) each including one of the first module 10, the second module 20, and the third module 30, or, when a single module (e.g., the first module 10) includes two or more unit modules, the apparatus setup may be divided into a plurality of sections each including the first-first module 11, the first-second module 12, and the first-third module 13.

FIG. 3 shows a CO according to an embodiment of the invention₂Cross section of a separation membrane device. Hereinafter, for convenience of description, for each region, CO will be contained₂Is referred to as an injection pipe, and relatively high CO having permeated through the separation membrane of the respective region₂The line from which the concentrated gas is discharged is called the permeate line and will have a relatively low CO without permeating through the separation membrane of the respective zone₂The conduit from which the concentrated gas exits is referred to as the channel conduit. In addition, the partitioned regionThe domain is denoted as the area (i) to be measured below.

Referring to FIG. 3, an exemplary CO₂The separation membrane device may be formed of a first module 10, a second module 20 and a third module 30. The first module 10 may be a multi-stage module formed of unit modules including a first-first module 11, a first-second module 12, and a first-third module 13, and each of the second and

third modules

20 and 30 may be a single-stage module formed of a single unit module. In this case, for example, the apparatus may be divided such that each area includes a single unit module. When the apparatus is divided into two or more areas in this manner, the area i (a) may be set to include the first-first module 11, the area i (b) may be set to include the first-second module 12, the area i (c) may be set to include the first-third module 13, the area i (d) may be set to include the second module 20, and the area i (e) may be set to include the third module 30, respectively.

After the apparatus is divided into two or more regions in this manner, a fourth reference value for each region may be calculated based on equation 4 to determine whether an abnormal situation has occurred according to the region. CO when determining whether an abnormal situation has occurred in a region₂The separation membrane device abnormity detection system can measure the flow rate and CO of the injection pipeline, the permeation pipeline and the channel pipeline of each area₂Concentration and pressure and using the measured flow rate, CO₂The concentration and the pressure to calculate a fourth reference value.

[ formula 4]

Fourth reference value { | (C)_PV,i-C_P·CO2,i)│/C_P·CO2,i}

In the formula 4, C_PV,iRepresenting CO measured in the permeate line of the area (i) to be measured₂Concentration (% by volume) and C_P·CO2,iRepresents CO in the permeation tube of the area to be measured calculated using the following equation 5₂And (4) predicting the concentration.

[ formula 5]

C_P·CO2,i＝A×C_M·CO2,i+B-{D×(C_M·CO2,i)²+E×C_M·CO2,i+F}^0.5

In the formula 5, C_M·CO2,iRepresenting the average CO on the surface of the separation membrane in the region (i) to be measured₂Concentration (% by volume), and A, B, D, E and F are constants calculated by the following equations 6 to 10.

[ formula 6]

A＝P/2

[ formula 7]

B＝(S+P-1)/{2×(S-1)}

[ formula 8]

D＝P²/4

[ formula 9]

E＝{P×(S-P+1)}/{2×(1-S)}

[ equation 10]

F＝(S+P-1)²/{4×(S-1)²}

In equations 6 to 10, P and S are values calculated using

equations

11 and 12 below.

[ formula 11]

P＝P_F,i/P_P,i

[ formula 12]

S＝P_CO2 ^G/P_N2 ^G

In

equations

11 and 12, P_F,iRepresenting the pressure (bar) in the line of the injection line of the area (i) to be measured; p_P,iRepresenting the pressure (bar) in the conduit of the permeation conduit of the area (i) to be measured; p_CO2 ^GCO representing the separation Membrane in the region (i) to be measured₂Permeability (GPU); and P_N2 ^GN representing the separation membrane in the region (i) to be measured₂Permeability (GPU).

Furthermore, the CO of the present invention₂The separation membrane device abnormality detection system can calculate the average CO on the surface of the separation membrane in the above equation 5 using the following equation 13₂Concentration (vol%) (C)_M·CO2,i)。

The prior art has the following defects: since it is difficult to measure the average CO on the surface of the separation membrane in situ₂Concentration (C)_M·CO2,i) And the value must be determined in the following mannerAnd (3) calculating: for each separation membrane, the permeability, thickness, etc. of the separation membrane are measured separately at an experimental level, and then a complicated computer operation (in which the measured permeability, thickness, etc. are applied according to the configuration of the apparatus) is performed, so that the resultant value of the change in the operating conditions of the apparatus cannot be predicted, and the complicated computer operation must be re-performed each time the conditions are changed.

In another aspect, the CO of the present invention₂The separation membrane device abnormality detecting system can easily use not only the following equation 13 according to the measured flow rate, CO₂Concentration and pressure obtaining an average CO on the surface of a separation membrane that is difficult to measure₂Concentration (C)_M·CO2,i) It is also possible to provide a calculated value very similar to the result obtained by actually performing a complicated experiment.

In addition, CO of the present invention₂The system for detecting abnormality of a separation membrane apparatus can solve the uncertainty of the result after the variation of the operating condition of the apparatus by the above equations 4 to 12 and 13.

[ formula 13]

C_M·CO2,i＝{(Q_F,i ^m+Pⁿ·C_F·CO2,i)×C_F·CO2,i}/(Q_F,i ^m+Pⁿ)

In equation 13, Q_F,iRepresenting the flow rate (Nm) in the injection line of the area (i) to be measured³Hr), and C_F,iCO in the injection line representing the area (i) to be measured₂Concentration (% by volume).

In equation 13, m and n are correction factors that can be obtained by fitting the above equations 5 to 12 to experimental data and operational data. The fitting is a process of applying the above equations 5 to 12 to the CO injected into the pipeline₂CO in permeate pipeline of concentration maps and operational data from modules and equipment₂Concentration maps to obtain parameters that minimize the error between the two maps. m and n can be calculated using any program without limitation as long as the program provides a curve fitting function. For example, the values calculated using the above equations 5 to 12 may be input to MATLAB,SigmaPlot, etc. to calculate m and n.

In equation 13, Q_F,i ^mAccording to the CO injected₂Is reflected on the CO on the surface of the separation membrane₂Increase in value, and P in the moleculeⁿIs a reflection of the CO as the volumetric flow rate of gas injected into each zone changes due to pressure changes₂The time change value of contact with the surface of the separation membrane. P in the denominatorⁿIs in contact with the residual CO in the module₂A flow rate dependent correction term. PⁿAnd C_F·CO2,iIs a ratio, and Q_F,i ^mIs a unit number with flow rate. However, due to Q_F,i ^mExist in both the denominator and the numerator of equation 13, and thus Q_F,i ^mMay be used in the form of dimensionless coefficients.

FIGS. 4 to 7 show the average CO in the permeate cell calculated by practical experiments₂A graph comparing the concentration with the predicted performance index value calculated according to the above equations 5 to 13. In each graph, the measured values and the calculated values according to equations 5 to 13 show a similar tendency to the experimental values. Therefore, it is confirmed that relatively accurate performance prediction can be performed using equations 5 to 13.

When the fourth reference value calculated according to equation 4 is about 10% or less, it may be determined that an abnormal situation has occurred in the region other than the corresponding region (i) to be measured. In this case, when the fourth reference value calculated in all the regions to be measured is about 10% or less, a process may be performed in which a leak site is detected in a portion of the pipe that is not directly connected to the region to be measured in the apparatus, the detected leak site is repaired, and it is confirmed whether the apparatus has reached a normal state.

Meanwhile, when the calculated fourth reference value exceeds about 10%, it may be determined that an abnormal situation has occurred in the corresponding region (i) to be measured, and it may be checked whether interference has occurred in the corresponding region (i) to be measured.

Specifically, checking whether interference has occurred in the area (i) to be measured may include: when one or more of the fifth reference value calculated using equation 14 and the sixth reference value calculated using equation 15 is about 10% or more, it is determined that noise occurs due to interference.

[ formula 14]

A fifth reference value { | (CO permeating the pipeline before 10 seconds)₂Concentration measurement-current CO of permeate line₂Concentration measurements) — (CO permeated through the pipeline before 10 seconds)₂Concentration measurement) } × 100

[ formula 15]

A sixth reference value { | (flow rate measurement value of permeate line before 20 seconds-current flow rate measurement value of permeate line)/(flow rate measurement value of permeate line before 20 seconds) } × 100

When it is determined that noise has occurred in the course of checking whether interference has occurred in the region (i) to be measured, the controller may re-perform the calculation using the above equation 1 to calibrate the operation state of the apparatus.

When it is determined that noise has occurred in the course of checking whether interference has occurred in the region (i) to be measured, the controller may recalculate the second reference value and the third reference value according to the above equations 2 and 3 to calibrate the operation state of the apparatus.

When both the fifth reference value and the sixth reference value are less than about 10%, it may be determined that the region to be measured (i) is in an abnormal operation state, and the abnormal operation may be solved by generating a countermeasure. In this case, a more specific plan for solving the abnormal operation can be proposed using the above-described second reference value and third reference value.

In a specific embodiment, the measured CO in the permeation cell when the fifth reference value and the sixth reference value are both less than about 10 percent₂Concentration lower than target CO₂Concentration (K) and CO in the osmosis unit₂The capture rate is higher than the target CO₂At the capture rate (J), CO₂The system for detecting abnormality of a separation membrane apparatus includes a system for solving an abnormal operation by checking whether a leak has occurred in a pipe connected to a corresponding region in which the abnormal operation is detected. The formula { (Q) can be used_P×C_P·CO2)/(Q_IN×C_IN·CO2) X 100 to calculate CO in the permeate cell₂The capture rate.

In another embodiment, when the fifth reference value and the sixth reference value are both less than about 10%, the CO measured in the permeation cell₂Concentration equal to target CO₂Concentration (K) and CO in the osmosis unit₂Capture rate lower than target CO₂At a capture rate (J), CO₂The separation membrane plant abnormality detection system may include solving an abnormal operation by checking whether pipes connected to an inlet unit, a permeation unit, and a residue unit of the plant have leaked and by checking whether a valve of each pipe is opened.

In yet another embodiment, when the fifth reference value and the sixth reference value are both less than about 10%, the CO measured in the permeation cell₂Concentration higher than target CO₂Concentration (K), and CO in the osmosis unit₂Capture rate lower than target CO₂At a capture rate (J), CO₂The separation membrane device abnormality detection system may include a device for detecting abnormality by checking CO connected to a corresponding region in which an abnormal operation is detected₂Whether the recirculation of the exhaust gas discharge pipe is performed in a normal state (whether the recirculation is performed in a normal state) is performed to solve the abnormal operation.

When the fifth reference value and the sixth reference value are both less than about 10%, the CO measured in the permeation cell₂Concentration higher than target CO₂Concentration (K) and CO in the osmosis unit₂The capture rate is higher than the target CO₂At a capture rate (J), CO₂The separation membrane device abnormality detection system may include a flow rate and CO measurement unit for measuring each of the inlet unit, the permeation unit, and the residue unit by inspection₂Whether the measurer of the concentration is in a normal state to solve the abnormal operation.

FIG. 1 shows a CO according to an embodiment of the invention₂An exemplary flow diagram of a separation membrane device anomaly detection system. This is merely an example, and the contents of the present invention are not limited thereto.

Referring to FIG. 1, an exemplary CO of the present invention₂The separation membrane equipment abnormity detection system measures flow rate and CO by a measurer₂Concentration (S10) and collecting the measured flow rate and CO₂And (4) concentration.

The collected information is transmitted to the controller and used to calculate a first reference value using the above formula 1 to determine whether the apparatus is in an abnormal operation state (S11).

In the determination, when the first reference value is about 95% or more, CO₂The separation membrane device abnormality detecting system determines the operation state of the device by using the second reference value calculated by formula 2 and the third reference value calculated by formula 3 (S12) and checks whether the target value is achieved by the device operation.

When the value calculated using the first reference value is less than 95% and thus it is determined that the apparatus is in the abnormal operation state, it is possible to omit the determination of whether the apparatus is in the abnormal operation state using the second reference value and the third reference value and immediately perform a countermeasure for solving the abnormal operation.

In this case, a suitable countermeasure may be to detect and repair a leak portion of the entire pipe included in the apparatus and to check whether the apparatus has reached a normal state (S17).

When the second reference value and the third reference value are both less than the set value designated by the user and thus normal, the system may determine that the operation condition of the equipment is normal and recalculate the first to third reference values at intervals of 5 to 30 minutes to periodically monitor the CO₂A separation membrane device (S13).

Meanwhile, when one or more of the second reference value calculated using equation 2 and the third reference value calculated using equation 3 exceeds a set value designated by a user, the system determines that the operation state of the apparatus is abnormal. In this case, the device may be divided into a certain number of regions to determine the presence of abnormality by region (S14).

The determination of the presence of an abnormality by region is performed by using the fourth reference value calculated by the above equation 4 (S14). When the calculated fourth reference value is about 10% or less, it may be determined that an abnormal situation has occurred in an area other than the corresponding area to be measured. In this case, when the fourth reference value calculated in all the regions to be measured is about 10% or less, a process may be performed in which a leak site is detected in a portion of the pipe that is not directly connected to the region to be measured in the apparatus, the detected leak site is repaired, and it is confirmed whether the apparatus has reached a normal state.

Meanwhile, when the calculated fourth reference value exceeds about 10%, it may be determined that an abnormal situation has occurred in a portion of the corresponding region, and it is checked whether interference has occurred in the corresponding region (S15). Whether interference has occurred is determined by calculating the fifth reference value and the sixth reference value using the above equations 14 and 15.

When a state in which noise has occurred in more than about 10% of the fifth reference value or the sixth reference value is detected while checking whether interference has occurred (S15), the controller may calibrate the operation state of the apparatus by performing recalculation using the above-described equations 2 and 3 (S18).

When a state in which no noise occurs in which the fifth reference value and the sixth reference value are about 10% or less is confirmed when checking whether interference has occurred (S15), the system may process abnormal operation using the measured information by the following manner (S16): by replacing the modules in the respective areas, replacing the separation membranes, checking whether a leak occurs in the pipeline, changing the operating conditions of the apparatus, etc.

The configuration and action of the present invention will be described in more detail below using preferred embodiments of the present invention. However, the following examples merely provide preferred embodiments of the present invention, and the present invention is not limited in any way by the following examples.

Modes for the invention

Examples

Examples 1 to 5

CO configuration according to FIG. 2₂After separation of the membrane apparatus, the measured variables were fitted by MATLAB program using the above-described equations 5 to 13 of the present invention, and 1.74 and 2.37 were obtained as m and n in equation 13, respectively. Further, while changing the flow rate and pressure in the apparatus as shown in table 1 below, CO in the permeation unit due to the change in the flow rate and pressure was predicted₂Concentrations, as shown in FIGS. 4-7.

TABLE 1

Variables of	Flow rate (NL/min)	Pressure (Bar)
			Example 1	70	1
Example 2	70	1.5
			Example 3	70	2
Example 4	50	2
			Example 5	88	2

Comparative examples 1 to 5

Configuring the CO as shown in FIG. 2₂After the membrane separation apparatus, the flow rate and pressure in the apparatus were simultaneously changed as shown in table 2 below, and CO in the permeation unit due to the change in the flow rate and pressure was actually measured₂The change in concentration is shown in FIGS. 4-7.

TABLE 2

As can be seen from FIGS. 4 to 7, the CO in the permeation units in comparative examples 1 to 5 was calculated by actual experiments₂The concentrations show a similar trend to the predicted performance index curves calculated according to equations 5-13 of the present invention for examples 1-5. Thus, it was confirmed that relatively accurate performance prediction can be performed using equations 5-13.

Furthermore, although comparative examples 1 to 5 cause inconvenience in that experiments have to be conducted to derive each value, examples 1 to 5 of the present invention provide the result values in the form of predicted performance index curves using equations 5 to 13, thereby having the effect of using the measured values to predict and provide the change in the operating efficiency due to the change in the variables.

(description of reference numerals)

100: entrance unit

200: osmosis unit

300: residue unit

10: first module

11: first-first module

12: first-second module

13: first-third module

20: second module

30: third module

Claims

1. Method for detecting carbon dioxide (CO)₂) A system for separating anomalies in a membrane plant, the system comprising:

inlet unit containing CO₂Through which the gas comprising CO enters₂Means for separating the membrane modules;

a separation membrane module including an inlet for introducing CO₂To each CO₂A separation membrane module and permeating the supplied gas through the CO₂Separating the membranes and respectively passing the gas having relatively high CO that has permeated through the membranes₂The concentrated gas is discharged to a first discharge port, and the gas having relatively low CO that does not permeate through the separation membrane is discharged₂The gas with the concentration is discharged to a second discharge port;

a permeation unit for discharging a gas having a relatively high CO content₂A concentrated gas that is discharged to the outside of the apparatus;

residue unit for discharging residue with relatively low CO₂A concentrated gas that is discharged to the outside of the apparatus;

a measurer for measuring a flow rate, CO, included in the inlet unit, the infiltration unit, and the residue unit₂Concentration and pressure information; and

a controller for determining the presence of an abnormality from the information collected by the measurer, wherein:

the controller detects an operation condition of the apparatus as an abnormal condition when the first reference value calculated using equation 1 is less than 95%; and

when the first reference value calculated using equation 1 is 95% or more, the controller calculates second and third reference values according to equations 2 and 3 to determine the operation state of the device:

[ equation 1]First reference value [ { (Q) [ ]_P×C_P·CO₂)+(Q_R×C_R·CO₂)}/(Q_IN×C_IN·CO₂)]×100

[ equation 2]]Second reference value ═ J- { (Q)_P×C_P·CO₂)/(Q_IN×C_IN·CO₂)×100}│

[ equation 3]]Third reference value ═ K-C_P·CO₂│；

Wherein, in formulas 1 to 3:

Q_INindicating access to the apparatus through the inlet unitContaining CO₂Flow rate of gas (c) in Nm³/hr；

Q_PRepresents the flow rate of gas discharged to the permeation unit in Nm³/hr；

Q_RRepresents the flow rate of gas discharged to the residue unit in Nm³/hr；

C_IN·CO₂CO representing the inlet unit₂Concentration in% by volume;

C_P·CO₂CO representing gas discharged to the permeation unit₂Concentration in% by volume;

C_R·CO₂CO representing gas discharged to the residue unit₂Concentration in% by volume;

j represents target CO₂Capture rate in%; and

k represents the target CO₂Concentration in% by volume.

2. The system of claim 1, wherein when the first reference value calculated using equation 1 is less than 95%, the controller detects the operation condition of the equipment as an abnormal situation and checks whether a leakage has occurred in a pipe of the equipment and whether the equipment has reached a normal state.

3. The system of claim 1, wherein the controller recalculates the first reference value at intervals of five to ten minutes when both the second reference value calculated using formula 2 and the third reference value calculated using formula 3 are less than or equal to a set value designated by a user.

4. The system of claim 1, wherein the controller divides the entire apparatus into two or more regions when one or more of the second reference value calculated using formula 2 and the third reference value calculated using formula 3 exceeds a set value designated by a user, and then calculates a fourth reference value that determines whether an abnormal situation has occurred per region for each region based on formula 4 below:

[ formula 4]]Fourth reference value { | (C)_PV,i-C_P·CO_2,i)│/C_P·CO_2,i}

Wherein, in formula 4, C_PV,iRepresenting CO measured in the permeate line of the area (i) to be measured₂Concentration (% by volume), and C_P·CO_2,iRepresents CO in the permeation line of the region to be measured calculated using the following equation 5₂A predicted value of concentration;

[ equation 5]C_P·CO_2,i＝A×C_M·CO_2,i+B-{D×(C_M·CO_2,i)²+E×C_M·CO_2,i+F}^0.5

Wherein, in formula 5, C_M·_CO2,iRepresenting the average CO on the surface of the separation membrane in the region (i) to be measured₂Concentration (% by volume), and A, B, D, E and F are constants calculated by the following equations 6 to 10;

[ equation 6] A ═ P/2

[ equation 7] B ═ (S + P-1)/{2 × (S-1) }

[ equation 8)]D＝P²/4

[ equation 9] E ═ { P × (S-P +1) }/{2 × (1-S) }

[ equation 10)]F＝(S+P-1)²/{4×(S-1)²}

Wherein, in equations 6 to 10, P and S are values calculated using the following equations 11 and 12;

[ equation 11)]P＝P_F,i/P_P,i

[ equation 12)]S＝PCO₂ ^G/PN₂ ^G，

Wherein, in equations 11 and 12:

P_F,irepresents the pressure in the line of the injection line of the area (i) to be measured, in bar;

P_P,irepresenting the pressure in the conduit of the permeation conduit of the area (i) to be measured, in bar;

PCO₂ ^Gto indicate a waitMeasuring CO of separation membrane in zone (i)₂Permeability in GPU; and

PN₂ ^Gn representing a separation membrane in the region (i) to be measured₂Permeability in GPU.

5. The system according to claim 4, wherein when the fourth reference value is 10% or less, the controller checks whether a leak has occurred in a pipe of the equipment and whether the equipment has reached a normal state.

6. The system according to claim 4, wherein when the fourth reference value exceeds 10%, the controller determines that the area to be measured (i) is in an abnormal operation state and checks whether interference has occurred therein.

7. The system of claim 6, wherein checking whether the interference has occurred includes determining that noise has occurred due to the interference when one or more of a fifth reference value calculated using equation 14 below and a sixth reference value calculated using equation 15 below is 10% or higher:

[ equation 14)]A fifth reference value { | (CO permeating the pipeline before 10 seconds)₂Concentration measurement-current CO of permeate line₂Concentration measurements) — (CO permeated through the pipeline before 10 seconds)₂Concentration measurement) } × 100

Equation 15 the sixth reference value { (-a flow rate measurement value of the permeate conduit before 20 seconds-a current flow rate measurement value of the permeate conduit) }/(a flow rate measurement value of the permeate conduit before 20 seconds) } × 100.

8. The system according to claim 7, wherein the controller recalculates the second reference value and the third reference value according to equations 2 and 3 when it is determined that noise has occurred due to interference in checking whether interference has occurred in the area to be measured (i).

9. The system according to claim 8, wherein the controller determines that the area to be measured (i) is in an abnormal operation state and generates a countermeasure when both the fifth reference value and the sixth reference value are less than 10%.

10. The system of claim 9, wherein the CO as measured in the permeation unit of the device₂Concentration lower than target CO₂Concentration (K), and CO in the osmosis unit₂The capture rate is higher than the target CO₂Capturing a rate (J), the countermeasure including solving the abnormal operation by checking whether a leak has occurred in a pipe connected to a corresponding region in which the abnormal operation is detected,

wherein CO in the permeation unit₂Capture Rate Using the equation { (Q)_P×C_P·CO₂)/(Q_IN×C_IN·CO₂) X 100.

11. The system of claim 9, wherein the CO measured while in the osmosis unit₂Concentration equal to target CO₂Concentration (K), and CO in the osmosis unit₂Capture rate lower than the target CO₂Capture rate (J), the countermeasure comprising solving an abnormal operation by checking whether leaks have occurred in the pipes connected to the inlet unit, the infiltration unit and the residue unit of the apparatus and by checking whether a valve of each pipe is open,

12. The system of claim 9, wherein the CO as measured in the osmosis unit₂Concentration higher than the target CO₂Concentration (K), and CO in the osmosis unit₂Capture rate lower than the target CO₂Capture rate (J), the countermeasure including checking CO connected to the corresponding region in which the abnormal operation is detected₂Whether the recirculation of the exhaust gas discharge pipe is performed in a normal state to solve the abnormal operation;

13. The system of claim 9, wherein the CO as measured in the osmosis unit₂Concentration higher than target CO₂Concentration (K) and CO in the osmosis unit₂The capture rate is higher than the target CO₂Capture rate (J), the countermeasure comprising measuring each flow rate and CO in the inlet unit, the permeate unit and the residue unit by inspection₂Whether the measurer of the concentration is in a normal state to solve the abnormal operation;